An optoelectronic device configured to operate at an electromagnetic radiation frequency having metal wire electrodes that are optically transparent as a result of the wires having an effective plasma frequency that is equal to or lower than the electromagnetic frequency at which the device operates. The effective plasma frequency of the wire is lowered by configuring the path of the wire between the terminal ends to be meandering, serpentine, U-shaped and in other non-linear configurations.
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1. A photoconductive detector configured to operate at an electromagnetic radiation frequency comprising:
one or more ribbons having a helically-coiled shape, said one or more ribbons having a cross-section comprising two metal wire electrodes sandwiching a semiconductor layer;
said metal wire electrodes having an effective plasma frequency when in a linear configuration, said effective plasma frequency greater than said electromagnetic frequency; and
said metal wire electrodes in a non-linear configuration, said non-linear metal wire electrodes having an effective plasma frequency that is equal to or lower than the electromagnetic frequency.
4. An optoelectronic device configured to operate at an electromagnetic radiation frequency comprising:
an array having one or more helical coiled ribbon photovoltaic cells arranged on a substrate;
each photovoltaic cell comprises a ribbon having a cross-section comprising two metal wire electrodes sandwiching a semiconductor layer;
said metal wire electrodes having an effective plasma frequency when in a linear configuration, said effective plasma frequency greater than said electromagnetic frequency; and
said metal wire electrodes in a non-linear configuration, said non-linear metal wire electrodes having an effective plasma frequency that is equal to or lower than the electromagnetic frequency.
2. The device of
5. The optoelectronic device of claim , further comprising:
a metal wire electrode having a first terminal end and a second terminal end and defining a path between said terminal ends; and
said path is configured as a serpentine path that creates a plurality of alternating magnetic fields that oppose electrical current in said metal wire electrode to decrease the effective conductivity of said metal wire electrode as compared to a linear path between said terminal ends.
6. The device of
10. The device of
11. The device of
12. The device of
13. The device of
14. The detector of
15. The optoelectronic device of
17. The optoelectronic device of
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This application claims priority to and the benefit of the filing date of U.S. provisional application Ser. No. 61/872,174 filed Aug. 30, 2013 and incorporated herein for all purposes.
Not applicable.
Not applicable.
Optical absorption in metals is a fundamental loss process, which is difficult to avoid. When metals are nanostructured, the loss is typically more significant as the surface area increases and the structural size becomes comparable to the penetration depth of optical fields. In particular, when surface plasmons—collective oscillations of electromagnetic fields and free electrons in metal surfaces—are excited, energy dissipation can become even greater.
The absorption in metals often limits the efficiency of metal-based nanoscale devices. For example, in optoelectronic devices, such as nanophotovoltaic devices, light absorption in metal electrodes does not lead to electricity and decreases the efficiency of the device. In light emitting diodes, surface plasmons can be exploited to concentrate light but strong metal absorption remains a major source of losses in plasmon-mediated devices.
The problem of this parasitic absorption becomes critical when ultra-high efficiency devices are desired. Moreover, if the device operates over a broad band as in solar cells, metal absorption needs to be controlled over the whole spectrum of interest and this poses challenges.
When high refractive index materials and metals are used in a device, inserting a thin low index material between them often reduces absorption loss in metals. Moreover, metals are typically opaque at visible frequencies of light and become transparent only at frequencies higher than their plasma frequency, which is typically in the ultraviolet region. This unique optical property of metals has its origin in their free electron gas. Below the plasma frequency, the free electrons follow the electromagnetic oscillation of light and prevent the light from penetrating into the metal.
Oppositely, above the plasma frequency, the light wave oscillation is faster than the electronic movement and light can propagate in the metal. In many optical and optoelectronic applications, the frequency of light is typically well below the plasma frequency of the metals involved and light can penetrate only a few tens of nanometers into the metals.
It is also known that nanostructured metal-dielectric composites can become transparent. However, in this case, it has not yet been clear if light takes paths in the dielectric materials or actually penetrates into the metal. Only in the latter case, it would be possible for light to go into the dielectric regions surrounded by the metal. This property would be extremely useful for certain applications such as photovoltaics where the nanostructured active materials can be surrounded by metal electrodes. However, in typical nanostructured photovoltaic devices, a large surface to volume ratio causes serious losses of electric charge carriers due to their surface recombination.
The various embodiments of the present invention provide methods and structures to render the nanostructured metals transparent using nanophotonic design. In one embodiment, optical absorption in metal nanostructures is reduced over a broad band by increasing the self-inductance of the structures. In other embodiments concerning metal nanocoil arrays, absorptance A is found to scale with self-inductance L as A∝Lα where α ranges from −0.5 to −1.5 at high frequencies. In a preferred embodiment, metal nanowires are combined with semiconductor strips so that the fraction of absorption in a semiconductor may increase by more than 60 times by coiling the composite strips due to increased self-inductance. This embodiment of the invention has uses in many metal-based applications that require low loss such as photovoltaics, solid state lighting, and transformation optics.
In another embodiment, the present invention provides non-linear nanostructured metal electrodes that reduce optical losses on flat surfaces. The embodiment concerns two-dimensional structures, which can be fabricated on flat surfaces. In this embodiment, an optoelectronic device that is configured to operate at an electromagnetic radiation frequency includes a non-linear metal wire electrode that has an effective plasma frequency that is equal to or lower than the electromagnetic frequency at which the device is designed to operate. The non-linear configuration of the wire increases self-inductance so that the free electrons in the metal become effectively heavy in response to high frequency light. The heavy electrons do not easily follow the electromagnetic oscillations and the electrode becomes more transparent exhibiting low loss.
This description is not to be taken in a limiting sense, but is made merely for the purpose of illustrating the general principles of the invention. The scope of the invention is defined by the appended claims.
In one preferred embodiment, the present invention provides an optoelectronic device that decreases absorption in metal nanostructures over a broad band. The invention utilizes the control of self-inductance to hinder the change in the movement of free electrons in metals to increase effective electron mass. For the monolayer array of metal coils 100 shown in
p=2πR tan θ, (1)
where π/2−θ is the angle between the wire and the coil axis (z-axis) and θ is assumed to be small so that tan2θ<<1.
As shown in
To impose boundary conditions on the fields, unit vectors ŝ and {circumflex over (n)}, which are parallel and normal to the side of the wire, were consider respectively. These are related to cylindrical coordinates by ŝ=−cos θ{circumflex over (Φ)}+sin θ{circumflex over (z)} and {circumflex over (n)}=sin θ{circumflex over (Φ)}+cos θ{circumflex over (z)}. Using the boundary conditions Em·ŝ=Eα·ŝ and εmEm·{circumflex over (n)}=Eα·{circumflex over (n)} where εm is the metal dielectric function, it is obtained
−Em,Φ cos θ+Em,z sin θ=−Eα,Φ cos θ+Eα,z sin θ (2)
and
εmEm,Φ sin θ+εmEm,z cos θ=Eα,Φ sin θ+Eα,z cos θ. (3)
The potential drop over the pitch p should be constant so that
Em,zl+Eα,z(p−l)=Eαp, (4)
where l is the width of the wire in the {circumflex over (z)} direction. It is well-known that, by Amperes law, the Hz field inside the coil is jΦδl/p where j is the electrical current density and δ(R) is the wire thickness. Thus, as shown in
where it is assumed e−iωt dependence of the fields with angular frequency ω. Equations (2)-(5) may then be put in a matrix form:
where
and Equation (1) is used and Ohm's law jΦ=σEm,Φ with σ being electrical conductivity. This time-dependent conductivity is related to the direct current conductivity σ0 by σ=σ0/(1−iωτ), where τ is the relaxation time. When the frequency is well below the plasma frequency of the metal, it can he assumed that |εm|1. In this case, Equation (6) can be solved to give:
Because it is assumed that Em is uniform along the wire, the absorptance A of the coil array can be obtained as:
where V is the volume of the wire in a unit cell, S=ap is the surface area of a unit cell exposed to light ε″m is the imaginary part of εm, and E0 is assumed to be the same as the incident field.
which is obtained from Equations (7) and (8) with α→0 and ε″m→σ0/(ε0ω). At high frequencies, absorptance scales with ω−2. This is associated with the fact that ε″m∝ω−3 when ωτ1 for Druck metals and |α|tan θ becomes comparable to or even larger than p approaching a constant value as the frequency increases. Also, α/p is related to the self-inductance of the coil by:
where L≡μ0/(4π tan2θ) is the self-inductance per unit length of the coil. Defining the effective relaxation time τeff≡τ+δlσ0L tan θ and, if ωτ1, or >1, it is obtained from Equations (7), (8), and (10) that A∝ω−2 L−3/2 for τeff2τ and A∝ω−2 L−1/2 for τeff2τ. Thus it is shown that the suppression of absorption at high frequencies in
The absorption decrease is directly related to the effective dielectric function εeff of the coil array. The εeff is obtained from
where the effective conductivity σeff relates to the volume average current jz and E0 by jz=σeffE0. Because jz=fjz=fσEm,z by Ohm's law where f=δl[1−δ/(2R)]/(α2tan θ) is the filling fraction of the metal nanocoil, the effective conductivity becomes σeff=fσEm,z/E0. Using Equation (10) and the solution of Equation (6) for Em,z/E0 in this expression, when |εm| is large, it is found:
where
σ0,eff=fσ0 tan2 θ (13)
is the effective conductivity at vanishing frequency. Plugging Equation (12) into Equation (11), εeff is evaluated for the model structure and compare to the values extracted from numerical calculations using Phys. Rev. B 2002, 65, 195104 in
Because self-inductance measures the tendency to oppose a change in the movement of the conduction electrons in the metal nanocoil by Lenz's law, the electrons behave as if their mass is enhanced by self-inductance. The effective mass of electrons, meff, is obtained by considering:
where neff=fn is the effective electron density. From Equations (13) with σ0=n e2τ/m and Equation (14), the enhancement of the effective mass becomes:
This enhancement factor scales with self-inductance as meff/m∝Lβ where β ranges from 1 to 3/2 depending on the relative magnitude between τeff and τ. For the example structure of
The effect of absorption reduction by heavy electrons has applications in nanoscale devices and optoelectronic devices where metals are combined with other materials. For example, in optoelectronic devices, metal structures are used as electrodes on active materials and all metallic parts need to be connected to each other to support electric current. In these cases, absorption loss in metals should be minimized while enhancing absorption in the active materials. Thus, in one embodiment, as shown in
Where λmin=2 μm, λmax=7.3 μm, and As and Am are partial absorptance in the semiconductor and metal, respectively.
This demonstrates that by controlling the self-inductance in metal nanostructures used with an optoelectronic device the efficiency of the device may be increased. In one application, a nanocoil array as shown above may be deployed wherein a semiconductor strip 302 is used with metal electrodes 303 and 304.
Moreover, the plasma frequency ωρ of a metal is given by
where n is the electron density, m the effective mass of electrons, e the electronic charge, and ε0 the permittivity of vacuum. When a metal is nanostructured with a periodicity much smaller than the wavelength of light and the metallic parts are all connected, the metallic structure behaves like a homogeneous medium and its optical property can be characterized by the effective plasma frequency ωρ,eff:
where n and m in Equation (17) are replaced by their effective values neff and meff, respectively. Also, neff is given by f∘n where f is the metal filling fraction and meff is a function of the structural geometry. The effective plasma frequency of a periodically nanostructured metal can be much lower than the plasma frequency of the homogeneous metal due to two mechanisms: the effective density of electrons is decreased by a low metal filling fraction and the effective mass of electrons increases due to a large self inductance. Self inductance measures the tendency of a metal wire to oppose a change in its current by magnetic effects and this increases the effective mass of electrons.
Even though the effective plasma frequency determines the optical properties of the nanostructured metal as a whole, the question of whether the light of a given frequency passes through the metallic parts inside the structure is not just answered by considering the effective plasma frequency. This effect of transparency in the metallic parts is associated with the movement of the elections in the metal and hence the effective electron mass meff, not with the effective electron density neff. Thus, for this effect, the self-inductance of the metal periodic structure should be large enough so that the electrons are effectively heavy enough and cannot follow the electromagnetic oscillation. Even if the effective electron mass is not large enough, the light can still pass through the metal more effectively than the case of a homogeneous metal when the thickness of the metallic part of the nanostructure is comparable to or less than the penetration depth of the metal.
In yet another embodiment of the invention, a helical coil photovoltaic cell 400 is shown in
The wavelength of light is 5 μm, which is much larger than the coil diameter of 1 μm. The diameter and the periodicity in the y-direction of the helical and the tube cell are 1 μm and 1.5 μm, respectively. Light of wavelength 5 μm is polarized along the x-axis is incident from the top along the z-axis. The unit cells are periodic in the x and y directions and the dimension unit is in meters. A 20 nm thick InSb cell is sandwiched between the electrodes, which are 10 nm thick each.
For comparison, a planar sheet and a tube array were also considered. The thicknesses of the metal and the semiconductor layer of these arrays are the same as in the helical ribbon. The planar sheet consists of metal-semiconductor-metal multilayers and the tube has the same diameter as the helical ribbon. The periodicity of the coiled ribbon and the tube arrays is also the same. The light is incident in the normal to the surface of the ribbon array, tube array, and the sheet.
To fabricate coiled structures and build devices out of them, self-coiling of patterned multilayer films may be used. This method uses thin crystalline semiconductor bilayers with internal stress due to lattice mismatch and/or other thin isotropic layers such as metals. The internal stress is highly anisotropic and cutting the multilayer film into strips can form nanoribbon helices, such that the strip axis is tilted from the principal force direction of the internal stress.
For photovoltaic applications, the metals act as electrodes that may have terminal ends that are connected to an electrical circuit to produce electric power. In this case, the metal electrodes will collect the charges generated in the semiconductor layer shortly after being separated at the pn-junction with negligible recombination at the surfaces. Since the present invention is capable of rendering metals transparent, it provides solutions to the problem of surface recombination in nanostructured photovoltaic materials. Moreover, the transparent metals can potentially replace transparent conducting oxides, which are relatively expensive and brittle, and have a large electrical resistance.
Another embodiment of the present invention concerns reducing optical losses in nanostructured metal electrodes on flat surfaces. In this embodiment, optical absorption in metal nanowire electrodes are integrated with active layers in optoelectronic devices. Microscopically, the free electrons in the metal become effectively heavy in response to high frequency light when the metal structure bears a large self-inductance. These heavy electrons do not easily follow the electromagnetic oscillations and the electrode becomes more transparent exhibiting low loss. It has been found that this same principle may also be realized in two-dimensional structures, which can be fabricated on flat surfaces.
In the various embodiments of the invention, the metal nanowire electrode has terminal ends with a configuration that defines a non-linear path between the terminal ends. Suitable path geometries that may be used in accordance with the invention include serpentine, U-shaped, meandering and other configurations known to those of skill in the art.
One preferred embodiment that defines a non-linear path is a repeating unit cell 600 as shown in
As shown in
In addition, as a result of changing the direction of the current flowing in the wire, alternating magnetic fields are created. The magnetic fields oppose electrical current in the metal wire electrode increasing self-inductance.
To determine if the optical properties of the serpentine structures outperform other conventional structures such as a linear or straight wire, transmittance and absorptance were calculated for both the non-linear and straight nanowire structures when the area fraction of the metal wire of w=20 nm is fixed at 0.2.
Nanostructuring does not necessarily reduce the optical loss. For example, the straight nanowire structure shows ˜48% loss which is even larger than that of the macroscopic counterpart. When the nanowire is slightly meandering, absorption loss increases initially while reflection decreases. Only when the structure is carefully designed, both absorption and reflection losses are expected to decrease. For a serpentine structure with l=240 nm, the total loss is only ˜3%.
A reduction in optical losses by varying the geometry of the nanowire may also be achieved when the wire is on a substrate, which is typical in optoelectronic devices. The absorptance in the metal nanowires when it is on a substrate is shown in
Reflectance spectra shown in
When an antireflection coating that covers both the metal nanowires and the substrate is present, reflection loss can be minimized. When it is negligible, the dominant loss will be due to absorption. In this case, with the non-linear, serpentine metal nanowires, the absorption loss would be very small. Thus, metal nanowire electrodes having non-linear path configurations, such as a serpentine path, exhibit almost negligible optical losses even with coverage of 20%, while the macroscopic counterparts would have ˜20% optical losses.
The results shown in
For this layered structure,
However, the transmittance into the substrate is higher or lower than the transmittance in
To determine the metal area fraction dependence of the losses, the transmission into InSb over the spectrum were averaged for the three different metal nanostructures at different area fractions as shown in
Even at a relatively large area fraction of 0.3, the optical losses due to the serpentine structure are only 0.065. While this loss is similar to that achieved with the smaller metal coverage structures where the periodicity was comparable to the wavelength, the sheet resistance RS of the serpentine structure is significantly higher. For the serpentine structure, the sheet resistance is Rs=ρ0α2f/(hw2)=430 Ω/sq where ρ0 is the DC resistivity of the metal modified by considering the surface and the grain boundary electronic scattering. This sheet resistance is similar to that of electrodes made of carbon nanotubes and graphenes, but the use of higher-conductivity metals such as silver or copper can reduce the sheet resistance.
In other embodiments, the present invention provides optoelectronic devices configured to operate at an electromagnetic radiation frequency. The devices comprise metal wire electrodes that may be made of materials such as Au, Ag, Al, Cu, and alloys such as TiAu. The metal wire has an effective plasma frequency when in a linear configuration, which is greater than the electromagnetic frequency of the device. When acting as an electrode, the metal wire electrode is configured into a non-linear configuration so as to create an effective plasma frequency that is equal to or lower than the electromagnetic frequency of the device.
In other embodiments, metal wire electrodes may be configured as coils, which may also be helically coiled ribbons. The coil or coils may have a diameter equal to or less than 1 micron and a periodicity equal to or less than 1.5 microns. The winding angle may be equal to or less than 12 degrees.
In an alternate embodiment, the optoelectronic device is as helically coiled ribbon photovoltaic cell having a ribbon that is helically-coiled shape and the ribbon has a cross-section comprising two metal electrode layers sandwiching a semiconductor layer that may be InSb, InAs, GaSb, PbS, HgCdTe, HgZnTe, PbSe, PbTe, Bi2Te3 or GaSb/InAs superlattices. The semiconductor layer may also include a pn-junction, which may comprise InSb.
Additional embodiments include a device that may be an array of multiple helical coiled ribbon photovoltaic cells periodically arranged to form a monolayer coiled ribbon array on a substrate. Each photovoltaic cell comprises a ribbon having a helically-coiled shape. The ribbon may have a cross-section comprising two metal electrode layers sandwiching a semiconductor layer that includes a pn-junction.
The optoelectronic device of the present invention may further comprise a metal wire electrode having a first terminal end and a second terminal end that defines a path between the terminal ends. The path may be configured as a non-linear path that decreases the effective conductivity of the metal wire electrode as compared to a linear path between the terminal ends.
Other embodiments include configuring the path to have an inductance that is greater than the inductance of a linear wire. This path may be U-shaped or even a serpentine path that is U-shaped. The serpentine path may also be comprised of linear segments, which may further be connected at right angles.
In other embodiments, the optoelectronic device has absorption and reflection loss that is equal to or no more than 3 percent. The spectral average absorption and reflection loss is equal to or more than 3 percent. In other embodiments, the metal wire electrode covers up to 30 percent of a substrate and the absorption and reflection loss is equal to or no more than 3 percent.
While the present invention has a potential to be widely used for scientific assessment and management, the foregoing written description of the invention enables one of ordinary skill to make and use what is considered presently to be the best mode thereof. Those of ordinary skill will understand and appreciate the existence of variations, combinations, and equivalents of the specific embodiment, method, and examples herein. The invention should therefore not be limited by the above described embodiments, methods, and examples, but by all embodiments and methods within the scope and spirit of the invention as claimed.
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